CN113234309A - Preparation method of PLA (polylactic acid) reinforced powder with flame retardant effect - Google Patents
Preparation method of PLA (polylactic acid) reinforced powder with flame retardant effect Download PDFInfo
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- CN113234309A CN113234309A CN202110672063.1A CN202110672063A CN113234309A CN 113234309 A CN113234309 A CN 113234309A CN 202110672063 A CN202110672063 A CN 202110672063A CN 113234309 A CN113234309 A CN 113234309A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 68
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000000843 powder Substances 0.000 title claims abstract description 56
- 230000000694 effects Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000004626 polylactic acid Substances 0.000 title description 45
- 229920000747 poly(lactic acid) Polymers 0.000 title description 44
- 238000002156 mixing Methods 0.000 claims abstract description 52
- 239000000654 additive Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000008367 deionised water Substances 0.000 claims abstract description 32
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 32
- 230000000996 additive effect Effects 0.000 claims abstract description 29
- 239000007822 coupling agent Substances 0.000 claims abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003365 glass fiber Substances 0.000 claims abstract description 23
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 22
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 22
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 20
- 239000003085 diluting agent Substances 0.000 claims abstract description 20
- 229920001896 polybutyrate Polymers 0.000 claims abstract description 20
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 20
- BHTBHKFULNTCHQ-UHFFFAOYSA-H zinc;tin(4+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Sn+4] BHTBHKFULNTCHQ-UHFFFAOYSA-H 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims description 58
- 238000000034 method Methods 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 6
- 229920000642 polymer Chemical class 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical class BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- QHWKHLYUUZGSCW-UHFFFAOYSA-N Tetrabromophthalic anhydride Chemical class BrC1=C(Br)C(Br)=C2C(=O)OC(=O)C2=C1Br QHWKHLYUUZGSCW-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N ortho-diethylbenzene Natural products CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 230000003014 reinforcing effect Effects 0.000 claims description 3
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 238000005728 strengthening Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- YVZATJAPAZIWIL-UHFFFAOYSA-M [Zn]O Chemical compound [Zn]O YVZATJAPAZIWIL-UHFFFAOYSA-M 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a preparation method of PLA reinforced powder with flame retardant effect, which comprises the following steps: step one, preparing the following components and raw materials in percentage by mass: 38-42% of high-rigidity PLA, 24-28% of PBAT, 18-20% of zinc hydroxystannate, 16-20% of diatomite, 13-17% of aluminum hydroxide, 8-12% of glass fiber powder, 5-7% of flame retardant, 4-6% of additive, 4-6% of polyurethane resin diluent, 2-6% of antioxidant, 0.5-0.9% of ethyl carbamate, 0.1-0.3% of coupling agent and the balance of deionized water. According to the invention, the mode of adding the raw materials in batches is adopted according to different properties of the raw materials, so that the phenomena of raw material agglomeration and difficult uniform mixing caused by the traditional one-time addition can be avoided, the production efficiency is further improved, the flame retardant effect is obvious, and the thermal stability is strong.
Description
Technical Field
The invention relates to the technical field of novel environment-friendly materials, in particular to a preparation method of PLA reinforced powder with a flame retardant effect.
Background
Polylactic acid (PLA) is a biodegradable plastic with the best comprehensive property developed in recent years, has no pollution to the environment at all, has good biodegradability, can be completely degraded by microorganisms in the nature after being used, finally generates carbon dioxide and water, does not pollute the environment, and meets the requirement of the world on environmental protection. However, polylactic acid has disadvantages such as low heat distortion temperature, low impact strength, poor toughness, no flame retardancy, and poor heat resistance, and thus does not meet the physical property requirements of engineering plastics, which greatly limits its application. In many applications, fire-retardant performance is a crucial factor, and the addition of proper flame retardant can improve the flame-retardant performance. The early halogen-containing flame retardant has high corrosion to equipment in the production process, generates dust and waste liquid pollution, is easy to separate out in the use process, generates toxic substances such as dioxin and the like, and pollutes the environment. At present, the research on flame retardants mainly focuses on the design and synthesis of organic substances or oligomers containing phosphorus, nitrogen, sulfur, and other elements, and the flame retardancy of polymer materials by blending or copolymerization methods.
The invention provides PLA reinforced powder with flame retardant effect and a preparation method of the PLA reinforced powder, which are developed and solved aiming at the problems.
Disclosure of Invention
The invention aims to solve the defects of low heat distortion temperature, low impact strength, poor toughness, no flame retardance, poor heat resistance and the like in the prior art, and provides a preparation method of PLA reinforced powder with a flame retardant effect.
A preparation method of PLA reinforced powder with flame retardant effect comprises the following steps:
step one, preparing the following components and raw materials in percentage by mass: 38-42% of high-rigidity PLA, 24-28% of PBAT, 18-20% of zinc hydroxystannate, 16-20% of diatomite, 13-17% of aluminum hydroxide, 8-12% of glass fiber powder, 5-7% of flame retardant, 4-6% of additive, 4-6% of polyurethane resin diluent, 2-6% of antioxidant, 0.5-0.9% of ethyl carbamate, 0.1-0.3% of coupling agent and the balance of deionized water;
step two, sequentially adding the high-rigidity PLA, the PBAT, the diatomite, the polyurethane resin diluent, a part of additive and a part of deionized water prepared in the step one into an internal mixer for internal mixing for 1-2h, adding the zinc hydroxystannate and the aluminum hydroxide prepared in the step one into the internal mixer for mixing for 20-40min, and uniformly mixing to obtain a mixed material A;
step three, adding the glass fiber powder prepared in the step one, the flame retardant, the ethyl carbamate and the rest deionized water into the mixed material A, continuously mixing until the solid is uniformly dispersed, adding the antioxidant, the coupling agent and the rest additives prepared in the step one after uniform mixing, continuously mixing, and uniformly mixing to obtain a mixed material B;
and step four, transferring the mixed material B into a screw rod extruder for extrusion molding, transferring the mixed material B into a ball mill for crushing at the rotating speed of 1200-1400r/min for 1-2h, sieving the mixed material B by a 60-100-mesh sieve, and then placing the mixed material B into a vacuum drying oven for drying at the temperature of 60-100 ℃ for 1-2h to obtain the PLA reinforced powder.
Preferably, in the first step, the following components and the raw materials in percentage by mass are prepared: 39-41% of high-rigidity PLA, 25-27% of PBAT, 18.5-19.5% of zinc hydroxystannate, 17-19% of diatomite, 14-16% of aluminum hydroxide, 9-11% of glass fiber powder, 5.5-6.5% of a flame retardant, 4.5-5.5% of an additive, 4.5-5.5% of a polyurethane resin diluent, 3-5% of an antioxidant, 0.6-0.8% of ethyl carbamate, 0.15-0.25% of a coupling agent and the balance of deionized water.
Preferably, in the first step, the following components and the raw materials in percentage by mass are prepared: 40% of high-rigidity PLA, 26% of PBAT, 19% of zinc hydroxystannate, 18% of diatomite, 15% of aluminum hydroxide, 10% of glass fiber powder, 6% of flame retardant, 5% of additive, 5% of polyurethane resin diluent, 4% of antioxidant, 0.7% of ethyl carbamate, 0.2% of coupling agent and the balance of deionized water.
Preferably, the volume ratio of the additive in the second step to the additive in the third step is 1: 1, the volume ratio of the deionized water in the step two to the deionized water in the step three is (2-3): 1.
preferably, the granularity of the glass fiber powder is 80-150 meshes, and the specific surface area of the diatomite is 55-60 m2/g。
Preferably, the additive is one or more of sodium bicarbonate, acetone, polyvinyl alcohol tert-butyl aldehyde, petroleum ether, diethyl ether or benzene.
Preferably, the high rigidity PLA has a weight average molecular weight of [ (1X 10)5)-(1×106)]g/mol。
Preferably, the coupling agent is a titanate coupling agent or a composite silane coupling agent, and the antioxidant is antioxidant 1010.
Preferably, the flame retardant is one of a bromine flame retardant, a phosphorus flame retardant and a nitrogen flame retardant.
Preferably, the brominated flame retardant comprises aromatic bromide flame retardant and/or aliphatic bromide flame retardant, and the brominated flame retardant is selected from one or more of brominated phenols, tetrabromophthalic anhydride, brominated styrene and polymers thereof, bromine-containing high polymer and oligomers thereof.
Compared with the prior art, the invention has the beneficial effects that: through the high rigidity PLA of rational ratio, PBAT is the base stock, add hydroxyl zinc stannate, diatomaceous earth and aluminium hydroxide have the effect of fire-retardant and suppression cigarette in coordination, and the fire retardant addition is less, reduce the production of harmful substance in the combustion process, and is environment-friendly, can not produce the foul smell, in addition cooperate glass fiber powder, additive, polyurethane resin diluent, add such as ethyl carbamate, improve the mechanical strength of the PLA reinforcing powder who makes on the one hand, on the other hand can accelerate the dispersion, and can the concurrent operation when producing, improve production efficiency. According to the invention, the mode of adding the raw materials in batches is adopted according to different properties of the raw materials, so that the phenomena of raw material agglomeration and difficult uniform mixing caused by the traditional one-time addition can be avoided, the production efficiency is further improved, the flame retardant effect is obvious, and the thermal stability is strong.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples.
Example one
The invention provides a preparation method of PLA reinforced powder with flame retardant effect, which comprises the following steps:
step one, preparing the following components and raw materials in percentage by mass: 38% of high-rigidity PLA, 24% of PBAT, 18% of zinc hydroxystannate, 16% of diatomite, 13% of aluminum hydroxide, 8% of glass fiber powder, 5% of flame retardant, 4% of additive, 4% of polyurethane resin diluent, 2% of antioxidant, 0.5% of ethyl carbamate, 0.1% of coupling agent and the balance of deionized water;
step two, sequentially adding the high-rigidity PLA, the PBAT, the diatomite, the polyurethane resin diluent, a part of additive and a part of deionized water prepared in the step one into an internal mixer for internal mixing for 1h, adding the zinc hydroxystannate and the aluminum hydroxide prepared in the step one into the internal mixer for mixing for 20min, and uniformly mixing to obtain a mixed material A;
step three, adding the glass fiber powder prepared in the step one, the flame retardant, the ethyl carbamate and the rest deionized water into the mixed material A, continuously mixing until the solid is uniformly dispersed, adding the antioxidant, the coupling agent and the rest additives prepared in the step one after uniform mixing, continuously mixing, and uniformly mixing to obtain a mixed material B;
and step four, transferring the mixed material B into a screw rod extruder for extrusion molding, transferring the mixed material B into a ball mill for crushing at the rotating speed of 1200r/min for 1h, sieving the crushed material with a 60-mesh sieve, putting the sieved material into a vacuum drying oven, and drying the sieved material for 1h at the temperature of 60 ℃ to obtain PLA reinforced powder.
Example two
The invention provides a preparation method of PLA reinforced powder with flame retardant effect, which comprises the following steps:
step one, preparing the following components and raw materials in percentage by mass: 39% of high-rigidity PLA, 25% of PBAT, 18.5% of zinc hydroxystannate, 17% of diatomite, 14% of aluminum hydroxide, 9% of glass fiber powder, 5.5% of a flame retardant, 4.5% of an additive, 4.5% of polyurethane resin diluent, 3% of an antioxidant, 0.6% of ethyl carbamate, 0.15% of a coupling agent and the balance of deionized water;
step two, sequentially adding the high-rigidity PLA, the PBAT, the diatomite, the polyurethane resin diluent, a part of additive and a part of deionized water prepared in the step one into an internal mixer for internal mixing for 1.2h, adding the zinc hydroxystannate and the aluminum hydroxide prepared in the step one into the internal mixer for mixing for 25min, and uniformly mixing to obtain a mixed material A;
step three, adding the glass fiber powder prepared in the step one, the flame retardant, the ethyl carbamate and the rest deionized water into the mixed material A, continuously mixing until the solid is uniformly dispersed, adding the antioxidant, the coupling agent and the rest additives prepared in the step one after uniform mixing, continuously mixing, and uniformly mixing to obtain a mixed material B;
and step four, transferring the mixed material B into a screw rod extruder for extrusion molding, transferring the mixed material B into a ball mill for crushing at the rotating speed of 1250r/min for 1.2h, sieving the crushed material with a 70-mesh sieve, putting the sieved material into a vacuum drying oven, and drying the sieved material for 1.2h at the temperature of 70 ℃ to obtain PLA reinforced powder.
EXAMPLE III
The invention provides a preparation method of PLA reinforced powder with flame retardant effect, which comprises the following steps:
step one, preparing the following components and raw materials in percentage by mass: 40% of high-rigidity PLA, 26% of PBAT, 19% of zinc hydroxystannate, 18% of diatomite, 15% of aluminum hydroxide, 10% of glass fiber powder, 6% of flame retardant, 5% of additive, 5% of polyurethane resin diluent, 4% of antioxidant, 0.7% of ethyl carbamate, 0.2% of coupling agent and the balance of deionized water;
step two, sequentially adding the high-rigidity PLA, the PBAT, the diatomite, the polyurethane resin diluent, a part of additive and a part of deionized water prepared in the step one into an internal mixer for internal mixing for 1.5h, adding the zinc hydroxystannate and the aluminum hydroxide prepared in the step one into the internal mixer for mixing for 30min, and uniformly mixing to obtain a mixed material A;
step three, adding the glass fiber powder prepared in the step one, the flame retardant, the ethyl carbamate and the rest deionized water into the mixed material A, continuously mixing until the solid is uniformly dispersed, adding the antioxidant, the coupling agent and the rest additives prepared in the step one after uniform mixing, continuously mixing, and uniformly mixing to obtain a mixed material B;
and step four, transferring the mixed material B into a screw rod extruder for extrusion molding, transferring the mixed material B into a ball mill for crushing at the rotating speed of 1300r/min for 1.5h, sieving the crushed material with an 80-mesh sieve, putting the sieved material into a vacuum drying oven, and drying the sieved material for 1.5h at the temperature of 80 ℃ to obtain PLA reinforced powder.
Example four
The invention provides a preparation method of PLA reinforced powder with flame retardant effect, which comprises the following steps:
step one, preparing the following components and raw materials in percentage by mass: 41% of high-rigidity PLA, 27% of PBAT, 19.5% of zinc hydroxystannate, 19% of diatomite, 16% of aluminum hydroxide, 11% of glass fiber powder, 6.5% of a flame retardant, 5.5% of an additive, 5.5% of polyurethane resin diluent, 5% of an antioxidant, 0.8% of ethyl carbamate, 0.25% of a coupling agent and the balance of deionized water;
step two, sequentially adding the high-rigidity PLA, the PBAT, the diatomite, the polyurethane resin diluent, a part of additive and a part of deionized water prepared in the step one into an internal mixer for internal mixing for 1.8h, adding the zinc hydroxystannate and the aluminum hydroxide prepared in the step one into the internal mixer for mixing for 35min, and uniformly mixing to obtain a mixed material A;
step three, adding the glass fiber powder prepared in the step one, the flame retardant, the ethyl carbamate and the rest deionized water into the mixed material A, continuously mixing until the solid is uniformly dispersed, adding the antioxidant, the coupling agent and the rest additives prepared in the step one after uniform mixing, continuously mixing, and uniformly mixing to obtain a mixed material B;
and step four, transferring the mixed material B into a screw rod extruder for extrusion molding, transferring the mixed material B into a ball mill for crushing at the rotating speed of 1350r/min for 1.8h, sieving the mixed material B by a 90-mesh sieve, putting the sieved mixed material B into a vacuum drying oven, and drying the sieved mixed material B for 1.8h at the temperature of 90 ℃ to obtain PLA reinforced powder.
EXAMPLE five
The invention provides a preparation method of PLA reinforced powder with flame retardant effect, which comprises the following steps:
step one, preparing the following components and raw materials in percentage by mass: 42% of high-rigidity PLA, 28% of PBAT, 20% of zinc hydroxystannate, 20% of diatomite, 17% of aluminum hydroxide, 12% of glass fiber powder, 7% of flame retardant, 6% of additive, 6% of polyurethane resin diluent, 6% of antioxidant, 0.9% of ethyl carbamate, 0.3% of coupling agent and the balance of deionized water;
step two, sequentially adding the high-rigidity PLA, the PBAT, the diatomite, the polyurethane resin diluent, a part of additive and a part of deionized water prepared in the step one into an internal mixer for internal mixing for 2 hours, adding the zinc hydroxystannate and the aluminum hydroxide prepared in the step one into the internal mixer for mixing for 40min, and uniformly mixing to obtain a mixed material A;
step three, adding the glass fiber powder prepared in the step one, the flame retardant, the ethyl carbamate and the rest deionized water into the mixed material A, continuously mixing until the solid is uniformly dispersed, adding the antioxidant, the coupling agent and the rest additives prepared in the step one after uniform mixing, continuously mixing, and uniformly mixing to obtain a mixed material B;
and step four, transferring the mixed material B into a screw rod extruder for extrusion molding, transferring the mixed material B into a ball mill for crushing at the rotating speed of 1400r/min for 2h, sieving the crushed material with a 100-mesh sieve, putting the sieved material into a vacuum drying oven, and drying the sieved material for 2h at the temperature of 100 ℃ to obtain PLA reinforced powder.
In the first to fifth embodiments, the volume ratio of the additive in the second step to the additive in the third step is 1: 1, the volume ratio of the deionized water in the step two to the deionized water in the step three is (2-3): 1. the granularity of the glass fiber powder is 80-150 meshes, and the specific surface area of the diatomite is 55-60 m2(ii) in terms of/g. The additive is one or more of sodium bicarbonate, acetone, polyvinyl alcohol tert-butyl aldehyde, petroleum ether, diethyl ether or benzene. The weight average molecular weight of the high-rigidity PLA is [ (1 x 10 ]5)-(1×106)]g/mol. The coupling agent is titanate coupling agent or composite silane coupling agent,the antioxidant is antioxidant 1010. The flame retardant is one of a brominated flame retardant, a phosphorus flame retardant and a nitrogen flame retardant. The brominated flame retardant comprises aromatic bromide flame retardant and/or aliphatic bromide flame retardant, and is selected from one or more of brominated phenols, tetrabromophthalic anhydride, brominated styrene and polymers thereof, bromine-containing high polymer and oligomers thereof.
Comparative example
Commercially available PLA materials are ball milled into powders.
The reinforced PLA powder prepared in the first to fifth examples and the PLA material of the comparative example were weighed to 200g, respectively, and the performance test was performed, wherein the test results are detailed in the following Table 1:
table 1 shows the results of the tests of the first to fifth examples and the comparative example
The results in table 1 show that the PLA reinforced powders prepared in the first to fifth examples of the present invention have excellent flame retardant effect, high tensile strength, and flame retardant property up to V-0, do not generate a droplet reaction after combustion, improve the use quality of the product, and are significantly better than the PLA materials on the market.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A preparation method of PLA reinforced powder with flame retardant effect is characterized by comprising the following steps:
step one, preparing the following components and raw materials in percentage by mass: 38-42% of high-rigidity PLA, 24-28% of PBAT, 18-20% of zinc hydroxystannate, 16-20% of diatomite, 13-17% of aluminum hydroxide, 8-12% of glass fiber powder, 5-7% of flame retardant, 4-6% of additive, 4-6% of polyurethane resin diluent, 2-6% of antioxidant, 0.5-0.9% of ethyl carbamate, 0.1-0.3% of coupling agent and the balance of deionized water;
step two, sequentially adding the high-rigidity PLA, the PBAT, the diatomite, the polyurethane resin diluent, a part of additive and a part of deionized water prepared in the step one into an internal mixer for internal mixing for 1-2h, adding the zinc hydroxystannate and the aluminum hydroxide prepared in the step one into the internal mixer for mixing for 20-40min, and uniformly mixing to obtain a mixed material A;
step three, adding the glass fiber powder prepared in the step one, the flame retardant, the ethyl carbamate and the rest deionized water into the mixed material A, continuously mixing until the solid is uniformly dispersed, adding the antioxidant, the coupling agent and the rest additives prepared in the step one after uniform mixing, continuously mixing, and uniformly mixing to obtain a mixed material B;
and step four, transferring the mixed material B into a screw rod extruder for extrusion molding, transferring the mixed material B into a ball mill for crushing at the rotating speed of 1200-1400r/min for 1-2h, sieving the mixed material B by a 60-100-mesh sieve, and then placing the mixed material B into a vacuum drying oven for drying at the temperature of 60-100 ℃ for 1-2h to obtain the PLA reinforced powder.
2. The method for preparing PLA reinforced powder with flame retardant effect as claimed in claim 1, wherein in the step one, the following components and their respective raw materials in mass percent are prepared: 39-41% of high-rigidity PLA, 25-27% of PBAT, 18.5-19.5% of zinc hydroxystannate, 17-19% of diatomite, 14-16% of aluminum hydroxide, 9-11% of glass fiber powder, 5.5-6.5% of a flame retardant, 4.5-5.5% of an additive, 4.5-5.5% of a polyurethane resin diluent, 3-5% of an antioxidant, 0.6-0.8% of ethyl carbamate, 0.15-0.25% of a coupling agent and the balance of deionized water.
3. The method for preparing PLA reinforced powder with flame retardant effect as claimed in claim 1, wherein in the step one, the following components and their respective raw materials in mass percent are prepared: 40% of high-rigidity PLA, 26% of PBAT, 19% of zinc hydroxystannate, 18% of diatomite, 15% of aluminum hydroxide, 10% of glass fiber powder, 6% of flame retardant, 5% of additive, 5% of polyurethane resin diluent, 4% of antioxidant, 0.7% of ethyl carbamate, 0.2% of coupling agent and the balance of deionized water.
4. The method for preparing PLA reinforced powder with flame retardant effect as claimed in claim 1, wherein the volume ratio of the additive in the second step to the additive in the third step is 1: 1, the volume ratio of the deionized water in the step two to the deionized water in the step three is (2-3): 1.
5. the method for preparing PLA reinforcing powder with flame retardant effect as claimed in claim 1, wherein the particle size of the glass fiber powder is 80-150 mesh, and the specific surface area of the diatomite is 55-60 m2/g。
6. The method for preparing a PLA strengthening powder with a flame retardant effect of claim 1, wherein the additive is one or more of sodium bicarbonate, acetone, polyvinyl alcohol t-butyl aldehyde, petroleum ether, diethyl ether or benzene.
7. The method for preparing a PLA reinforcing powder with flame retardant effect as claimed in claim 1, wherein the weight average molecular weight of the high rigidity PLA is [ (1 x 10 ]5)-(1×106)]g/mol。
8. The method for preparing a PLA reinforced powder with flame retardant effect as claimed in claim 1, wherein the coupling agent is titanate coupling agent or composite silane coupling agent, and the antioxidant is antioxidant 1010.
9. The method for preparing PLA reinforced powder with flame retardant effect as claimed in claim 1, wherein the flame retardant is one of brominated flame retardants, phosphorous flame retardants, and nitrogen flame retardants.
10. The method of claim 9, wherein the brominated flame retardant comprises aromatic bromide flame retardant and/or aliphatic bromide flame retardant, and the brominated flame retardant is selected from one or more of brominated phenols, tetrabromophthalic anhydride, brominated styrene and its polymers, bromine-containing polymers and oligomers.
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| EP2539396A2 (en) * | 2010-02-22 | 2013-01-02 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Composite composition, method for the production thereof, moulded part and use |
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